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Research
Synopsis:
Transition Metal
Chemistry:
Synthetic, mechanistic, and structural transition metal chemistry,
including applications to problems in catalysis, material science,
and medicine.
Our research interests are in the chemistry of the transition metals
and involve work in a number of allied areas. In relation to the
application of transition metals in catalysis we are interested
in the synthesis and reactivity of organometallic compounds which
may serve as models for the interaction of organic substrates with
heterogeneous transition metal catalysts.
As part of our work in this area we are investigating the reactions
of heteroatom- functionalized acetylenes with binuclear transition
metal complexes. We have discovered unusual 1,2-heteroatom shifts
in the reactions of acetylenes with bimetallic complexes of nickel,
palladium, and platinum which lead to the formation of bridged vinylidenes.
Such reactions are comparable to the well-known 1 ,2-hydride shifts
observed when acetylene is chemisorbed onto heterogeneous platinum
metal catalysts. Our work in the area of heterogeneous catalysis
is focused on the use of semiconductor materials in the photochemical
reactions of nitrogen compounds and is part of a collaborative effort
with Dr. Jimmie G. Edwards of this Department.
Throughout the course of our studies in these areas we rely on the
use of a variety of analytical methods to characterize the compounds
we synthesize and to investigate their reactivity in stoichiometric
and catalytic processes. In addition to the more routine analytical
techniques, we utilize both solution and solid-state multinuclear
magnetic resonance methods, FT-IR spectroscopy, GC-MS, X-ray crystallography,
and a variety of electroanalytical techniques.
Our interest in material science has led us to develop new synthetic
routes to molecular precursors to electroceramics. The molecular
precursors that we prepare have rigidly controlled stoichiometries
which lead to high purity, well-defined ceramic materials. We have
shown how the normally intractable material TiO2 can be converted
via a versatile molecular precursor,
[Ti(catecholate)3]2- , into materials such as BaTiO3, SrTiO3, BaxSr
yTiO3, PbTiO3, etc. Similar strategies may be employed in the synthesis
of ceramics based on bismuth, tin, germanium, etc.
In the application of transition metal chemistry to problems in
medicine, we have focused on the development of paramagnetic transition
metal complexes as contrast agents for magnetic resonance imaging
(MRI). we have shown that complexes of high-spin iron(III) with
catecholate ligands -- based on the naturally occurring catecholate
siderophores that bind iron -- have unusually high relaxivities
and that application of ligand design strategies and structure-activity
relationships allows the design of organ-selective MR contrast agents.
Our current focus in this area is the design of contrast media that
are capable of differentiation of tumors from normal parenchyma
in the liver, an approach that exploits the biochemistry of hepatocyte
uptake mechanisms.
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